JPS6021390A - Electrolysis using two phases electroconductive by electrolyte - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new electrolytic process, in particular for the precipitation and/or recovery of metals in the elemental state and for other redox reactions.

The electrolytic method provided by the present invention can be used for electrolytically depositing metals in the form of dendrites and for electroplating metals onto substrates, among other applications. . This electrolytic method can also be used to carry out chemical redox reactions, such as the oxidation or reduction of chemical species by electrolysis.

The method of the invention particularly uses an electrolyte system comprising at least two phases, one of which is aqueous, while the other phase is immiscible with the aqueous phase and in which case an interfacial Current passing is ionic rather than electronic.

Certain other two-phase electrolysis systems are already known.

For example, mercury electrolysers commonly used for the electrolysis of sodium chloride solutions to produce chlorine and sodium amalgams - ultimately sodium hydroxide - utilize two phases: aqueous sodium chloride solution and metallic mercury. however,
In this case, the mercury phase conducts by electrons, ie, by the movement of electrons as in any conductive metal. In fact, the mercury phase acts as a liquid cathode; moreover, in the sodium hydroxide-chlorine industry, electrolysis is used with two aqueous phases separated by an ion exchange membrane. In this regard, a sodium chloride solution forms the anolyte and generates chlorine at the anode in this anolyte. The electrolyte on the other side of the ion exchange membrane is an aqueous sodium hydroxide solution, and a cathode for generating hydrogen is present in this water bath. Therefore, these are both aqueous phases, and without an ion exchange membrane these aqueous phases would be miscible with each other. strictly limited.

A more general and well-known problem arises when dealing with the oxidation or reduction of water-insoluble species in organic electrochemistry in general. For example, electrolytic techniques are generally inadequate because organic liquids are generally nonconductive (dielectric). Generally, a way to overcome this difficulty to some extent is to use water-miscible co-solvents, such as ethanol or acetone, to co-dissolve the water-insoluble species in the aqueous phase. Another method is to use solubilizing compounds such as aromatic sulfonic acids. This solubilizing compound co-dissolves insoluble species and can also act as an electrolyte. Both of these methods create a single water-miscible phase for electrolysis, which also limits the application of these methods. For example, in 1973, Dekker (New York)
) published by M. M. O by Baizer
See rganic Electro-chemistry.

A new method has been found in which electrolysis can be carried out using two immiscible phases. One phase is aqueous and the other non-aqueous, but both phases conduct electricity by electrolysis.

That is, current passes between these two phases by the movement of ions rather than simply the movement of electrons.

The present invention therefore provides an inherently novel method for electrolysis. The method consists of passing an electric current between two electrodes through an at least two-phase electrolyte system, the electrolyte system containing as one phase an aqueous electrolyte solution;
The second phase also contains a water-immiscible liquid that serves as another electrolyte, with one electrode immersed alone in the aqueous electrolyte solution and the other electrode immersed alone in the water-immiscible liquid. This method involves soaking in water. This second non-aqueous phase generally comprises (at the temperature employed) a liquid containing, or consists of, or is substantially free of, an organic salt having at least some truly ionic character. Although constituted by the organic salt, the organic salt is substantially water-insoluble or at least preferentially substantially soluble in the organic solvent used to form the water-immiscible phase.

In contrast, although the aqueous phase typically includes solutions containing highly ionic salts, acids, or alkalis and may generally exhibit high conductivity or low resistivity, e.g., 5-10 ohm-cms, The non-aqueous, water-immiscible phase used therein typically exhibits a fairly high resistivity, for example on the order of 1000 ohm-cms. Thus, whereas electrolysis using a non-aqueous phase alone typically requires extremely high voltages, the method of the present invention allows the use of significantly lower cell voltages. Thus, one of the advantages of the present invention is that it allows systems that otherwise poorly conduct electricity to operate at practical and economically acceptable cell voltages.

Since the electrolyte phase, which is immiscible with the aqueous phase, is generally a very good solvent for other (organic) water-immiscible species, the present invention also applies to electrolytic redox reactions using water-miscible species. It can be used very easily. Thus, for example, tetraalkyl ammonium halostannite (
(which can be used as an electrolyte phase immiscible with the aqueous phase in the process of the invention) is a perfectly good solvent for various non-polar organic species, even for olefins such as ethylene. . If the electrolyte phase immiscible with the aqueous phase is a long-chain (e.g. C6-C24) carboxylate (e.g. sodium octylate), this phase also contains other (saturated or unsaturated) carboxylic acids, It is an excellent solvent for alcohols, etc.

The accompanying drawings illustrate two basic electrode cell arrangements that may be used in practicing the invention, as well as two presently preferred practical embodiments of the invention.

Considering first FIG. 2, a suitable cell container (either rectangular, cylindrical, or any other desired shape) 20 can be formed from a suitable material that is corrosion resistant and electrolytically stable, such as polypropylene. .

Suspended near the bottom of the cell 20 is an electrode 21 connected to an insulated current supply line 22 which will be connected to the cathode terminal of a DC power source as shown. In use, the cathode 21 is completely immersed alone in a phase 24 that is immiscible with the aqueous phase. An aqueous electrolyte, ie, an anolyte plate 25 having a relatively low specific gravity, is shown overlying the catholyte 24 with a liquid-liquid interface 26 between the anolyte and catholyte as shown. An anode 23 is suspended in the aqueous anolyte liquid phase and is connected by a power supply line 27 to a DC power source for the anode. The current is at the liquid-liquid interface 26
It will be understood that the signal passes between the two electrodes. In practicing the invention, such current passing is performed by ions.

The electrodes used in the aqueous electrolyte phase can be either cathodes or anodes, depending on the desired electrolysis method, and the electrodes in the non-aqueous phase are conversely anodes or cathodes.

If the phases have different specific gravity, one phase can float on top of the other simply with a liquid-liquid interface between the phases as shown in FIG. Separately, the two immiscible phases (anolyte and catholyte) are separated by an ion exchange membrane or a porous separator, e.g. ceramic or filter cloth.
can be separated, the phases being arranged in parallel.

In another practical embodiment described below, the anolyte is an aqueous phase suspended on a catholyte that is immiscible with the heavier aqueous phase.

Also, as in embodiments of the invention described below, one electrode may be a corrodible metal anode immersed in an aqueous anolyte, while the other electrode may be a non-corrosive metal anode immersed in a non-aqueous catholyte. It is an active cathode. If the anode, which can be corroded in this arrangement, is tin, for example, the electrode will corrode continuously during electrolysis, depositing tin dendrites on the cathode. Accordingly, one feature of the present invention is to provide a method for forming dendrite tin from large blocks of tin. Such dendrite tin is an important starting material for the production of organotin halides by direct reaction of tin with organohalides.

If tin is the anode, the catholyte may suitably be a water-miscible tin salt electrolyte. An example of such a salt is the general formula Ca
t + Sn It is a complex that

An example of RzQ+ is tetrabutylammonium.

Generally R is an organic hydrocarbyl group (or similar inert group containing a hydrocarbyl group with an inert substituent), the hydrocarbyl group forming the onium ion. Q represents N, P, As or Sb, in this case z is 4
and Q can be S or Se, in which case z
is 3. The compound represented by the general formula RzQX can be used, for example, as a catalyst or a reagent in the production of organotin halides. In addition, when used in this manner, a tin-containing halogenated stannite complex having the general formula RzQ+SnX-3, such as tetrabutylammonium bromostannite, is produced as a by-product.

The by-product formed during the direct reaction of tin with an organic halide in the presence of a compound of the general formula Cat+X- is particularly suitable as catholyte in the tin electrolysis process according to the invention.

Alternatively, if another metal is used as the anode that can be corroded, a complex of that metal will be formed by the Cat+X- species.

Thus, instead of using tin as the anode, for example an aluminum anode can be used as an alternative, with an aqueous solution containing aluminum trichloride and sodium chloride as the anolyte, the catholyte consisting of the general formula Cat+AlCl-4. is appropriate.

In still other systems, the anolyte may be e.g.
A lead anode is used with an aqueous solution containing a lead carboxylate and sodium chloride consisting of a 10 alkanoic acid, and the catholyte is a carboxylic acid solution containing a lead carboxylate. If, for example, scrap lead is used as the anode, the system allows recovery of the lead in the form of dendrites deposited on the cathode, for example on the lead cathode. Similarly, impure metals other than lead can be used as anodes, and metals other than lead can be obtained in purified form by this method (
(especially if the impure metal has an electrode potential significantly different from that of the metal being recovered).

Other such metals that may be used include standard electrode potentials (typically from about +1.5 volts to about -1.66 volts).
There are some metals that have a hydrogen electrode (relative to the standard hydrogen electrode), such as silver, gold,
Platinum, palladium, copper, lead, tin, nickel, cobalt,
Metals include indium, cadmium, iron, gallium, chromium, zinc, manganese, titanium and aluminum.

If lead is used, these other metals may also be used with appropriately selected Cat+X- species or as metal salts of long chain carboxylic acids. Of course, the choice of organic carboxylic acid used in forming the carboxylic acid salt is primarily dictated by the need to obtain an electrolyte system that is immiscible with the aqueous phase. That is, preferably the carboxylic acid metal salt and the carboxylic acid itself should be soluble in the aqueous phase to an extent of less than 10% at the temperatures used in the electrolytic process itself. Correspondingly, although there may be some water dissolved in the water-immiscible phase, the proportion of dissolved water is insufficient to disrupt the basic immiscibility and the inevitable separation of the two phases. If so, water does not pose a significant problem in practicing the invention. Generally, carboxylic acids having at least 6 carbon atoms are selected for this purpose. Similarly, any Rz
Regardless of the choice of the Q+ species and whatever anion is chosen, the basic requirements regarding immiscibility and solubility of the metal complex with the RzQ+ species and the anion must again be complied with.

Basically, the invention thus uses as one of its features a water-immiscible liquid phase, generally an organic liquid phase, which can actually be a solution and which can Although containing a high concentration of ionic species (and yet this liquid phase is substantially insoluble in water), such a phase is nevertheless relatively non-conductive, at least to the extent of the conductivity of the aqueous phase. It will be understood that

In contrast, it is desirable that the electrolyte in the aqueous phase be a highly conductive system, which is easily achieved, for example, by introducing suitable inorganic salts, as is already known in the art. be done. Alternatively, or in addition, alkaline or acidic aqueous phases may be used as such electrolytes in addition to salts.

Depending on the particular electrolytic process desired to be carried out, the particular choice of anolyte and catholyte systems will be determined according to the aforementioned principles.

Instead of a single anode, which can be corroded, such as tin, aluminum or lead, which is carried by electrolysis and deposited on the cathode, a three-anode system can be used as shown in FIG. .

In this system, the electrolytic cell 10 also includes an electrode 11 connected to a suitably insulated feed line 12 to a power source (although a negative power source is shown, if desired). can also be a positive power source), this cathode is completely immersed in a catholyte phase 13 that is immiscible with the aqueous phase (as shown). Above the catholyte phase 13 is an aqueous catholyte phase 14 with an interface 14a between the two phases. Also extending into the anolyte phase 14 is a compartment 15 having at least one wall member formed from an ion exchange membrane, which membrane is permeable to ions but separates the anolyte 16 and the anolyte 14 from each other. Do not mix. A non-corrosive anode 17 extends suitably into both chambers 15 and is also connected to a DC power supply. An erodible electrode 18 extends into the anolyte (hereinafter referred to as the "intermediate" anolyte in this embodiment) and is connected to a power supply by a power supply line 19. . As shown, electrodes 17 and 18 are both anodes.

In such a system, compartment 15 may contain an aqueous sodium hydroxide solution as anolyte 16, while intermediate anolyte 14 is conveniently an aqueous solution of a metal salt, e.g. a metal chloride, such as sodium chloride. . The catholyte 13 is a carboxylic acid metal salt solution in carboxylic acid or Cat
+X-, both of which are immiscible with the aqueous phase anolyte 14. Various metals can be used as the salt used in the anolyte 14, including without limitation cobalt, nickel, titanium, manganese, vanadium, and the like.

Among the methods enabled by the electrolytic cell of FIG. 1 is the recovery of elemental metals from dissolved salts of elemental metals. This salt would have subsequently been obtained as waste from an independent chemical process. The metal thus recovered can be used to produce various metal compounds including organometallic compounds. Such dissolved salts may be present either in a phase immiscible with the aqueous phase or in the aqueous phase or both, and the metal is reduced to its elemental state at the cathode.

In particular, because the electrolytic process of the present invention advantageously produces highly reactive metal species of the dendrites, the present invention is capable of producing the desired carboxylic acid directly from the metal of the formed dendrites and the desired carboxylic acid. Provides a means for forming metal salts (for use as paint driers, for example). The dendrite metal and carboxylic acid are heated with air or oxygen (outside the electrolytic cell). This air or oxygen dissolves the metal in the dendrites at an excellent reaction rate and reacts directly with the carboxylic acid, giving a high yield.

In the specific example of three electrodes shown in FIG. 1, when an alkali is used as the anolyte 16, it is necessary to maintain the balance of the total electrolytic reaction equation, so oxygen is added to the anode 17. Occur.

The two-phase electrolysis system of the present invention can also be used in electrolysis involving only organic species. Thus, for example, in the embodiment of FIG. 1 or 2, an inert anode 18 or 2, such as platinum,
3 can be used respectively.

This inert anode is suspended in an aqueous sulfuric acid solution with 14 or 25 anodes, respectively. This aqueous solution is in turn contacted at the interface with a water-immiscible phase comprising, for example, acrylonitrile, adiponitrile and a conductive species such as sodium carboxylate or tetraalkylammonium sulfonate or tetraalkylammonium sulfate. When these are electrolyzed, oxygen is generated at the anode, and hydrogenation dimerization of acrylonitrile occurs at the cathode to produce adiponitrile.

Other organic species can likewise be electrolytically reduced by the process of the invention, such as benzaldehyde to benzyl alcohol, benzyl to benzylidene, salicaldehyde to the corresponding alcohol, nitrophenol to hydroxyl, etc. Propyl bromide is obtained from aniline or from allyl bromide. When using acrylonitrile, other reductive dimerizations or reductive polymerizations, reactions using organics are carried out by electrolysis whenever the organic species suitable for such electroreduction is dissolved in the catholyte phase which is immiscible with the aqueous phase. It can be done even if

The electrolytic method of the present invention can also be used to electroplate alloys onto cathode substrates. For example, two or more metals may be used in an aqueous solution containing chlorides of these metals used as an anolyte and a water-insoluble chloride of these metals used as a catholyte, such as Bu4N+MCl-m (however, Bu4N+MCl-m)
is butyl, M is a metal, and m is the valence of the metal plus 1), and as an anode...separate metal anodes (i.e., two such as anode 23). It can be used either as a single alloy anode) or as a single alloy anode. If two different erodible anodes are used, the relative amount of metal deposited can be varied by the amount of current supplied to each of the anodes separately.

To further illustrate the practice of the invention, presently preferred embodiments of the invention are presented in the following Examples.

EXAMPLE The apparatus used in this example was the cell shown schematically in the accompanying drawing of FIG.

This cell consists of a polypropylene tank 10 measuring 40 cm x 40 cm x 25 cm, and an insulated power supply line 12.
35 cm x 25 cm x 0.3 cm stainless steel cathode 11 connected to the At the bottom of the cell is catholyte 1
3, tetrabutylammonium bromostannite (Bu4N+SnBr-3, Bu4NBr solution and HSn
Synthetically prepared from Br3 solution) (11 kg)
was loaded.

16 liters of a 20% NaBr aqueous solution was placed on top of this catholyte as an intermediate electrolyte 14. A box covered with an ion exchange membrane (Nafion, Dupont membrane) was immersed in the intermediate electrolyte. This box contained a NaOH solution 16 and a nickel anode 17. Further, the tin anode 18 held on the power supply line 19 was immersed in the intermediate electrolyte.

Anodes 17 and 18 were connected to the positive terminal of a variable power supply, and cathode feed line 12 was connected to the negative terminal. Current was passed through the cell over a period of 17 hours ranging from 40 amps at the beginning to 100 amps at the end. During this period the temperature within the cell increased by 75-85°. The cell pressure at the beginning was 19 volts, and this voltage gradually decreased to 5 volts at the end. 59 during this period
Six ampere-hours were passed through the tin anode 18 resulting in a loss of 1500 grams of tin. 540 amps for nickel anode 17
Time passed.

A combined anode current of 1136 amp-hours passed through the cathode 11 was made using fine dendrite tin powder (2513 g
) occurred. 1320 g of this tin product was obtained from the anode 18 and 1193 g from the catholyte 13. In this way, the final catholyte phase is composed of dendrite tin (25
13g), tetrabutylammonium bromide (323
8g) and unreacted tetrabutylammonium bromostannite (5040g).

Although in this example the catholyte was prepared as a special catholyte, a tin halide by-product complex could be used instead.

This complex is produced by directly reacting tin with an organic halide in the presence of a reagent amount of a compound represented by the general 2Cat+X-, for example, a compound represented by the general 2RzQ+X- as defined above. Formed during the production of chemical compounds. The overall reaction is stoichiometric 2Sn+3RX+RzQX→R3SnX+RzQSnX
3. At the end of the reaction, the organotin halide product is recovered by extraction into a hydrocarbon solvent;
A dark khaki by-product is left which is insoluble in hydrocarbons and insoluble in water. This by-product is RzQ-Sn
Contains X-3 or consists of RzQ+SnX-3. This is the tin halide byproduct complex, and this complex is used as the catholyte in this embodiment of the invention.

A description of such a method can be found in the patent application filed on January 6, 1982 entitled "Method for producing organotin halides".
For example, one of the practical cells suitable for this electrolysis invention is disclosed in Japanese Patent Application No. 752 and Japanese Patent Application No. 1982-753 for "Electrolysis of Tin Complex" filed on January 6, 1988. As shown in the figure. This cell is approximately 30cm x 30c
It comprises a polypropylene body 41 having a cross section of m and an overall height of about 45 cm. The cell includes a polypropylene bottom valve 42 and is mounted to a base (not shown) such that the inverted pyramid shape of the bottom extends through a hole in the support platform. The cell is heated and insulated by an external electrical heating tape 43 and is coated with a coating 4.
4. Place another two pieces of tape 4 on the relatively high part of the cell.
5 and 46.

The cell has two cathode plates 47 inside, and these cathode plates are connected to a cathode feed line 56.

Above the cathode are two tin anodes 48 (not shown), which are attached to a mild steel feed line 58. These feeders are in turn supported on insulated bushings on an anode support frame 49, which is screwed onto the platform.

Alongside the tin anode there is a third anode 50 made of nickel. The nickel anode is supported by a mild steel feed line 57 and is fixed from the anode support frame. The nickel inner electrode 50 is isolated from the rest of the cell inside a compartment formed by an outer fixing member 51, an inner member 52, and two ion exchange membranes 53. The sections 51 and 52 are U-shaped in cross-section and are secured to each other by bolts that sandwich the membrane 53 so that a five-sided compartment with an open top is formed.

The cell has two polypropylene scrapers 54 with blades 54a that can be forced across the surface of the cathode 47 to scrape and remove metal formed on the cathode. This metal can also be dropped to the bottom of the cell (ie, below the cathode). The cell is equipped with a stirrer on the shaft 55,
This shaft is connected to a motor (not shown). This stirrer is used to stir the bottom phase containing such metal particles.

During operation, the tin anode feed line 58 and the right cathode feed line 56 are connected to 1
A rectifier (not shown) follows, and the nickel anode feed line 57 and the left cathode feed line 56 are connected to another rectifier. The tin anodes can be adjusted up or down on their feed lines 58.

Already cited application “Method for producing organotin halides”
The cell was operated by charging 25.9 kg of the mixed tin halide complex by-product from the preparation of tributyltin bromide and 16 liters of 10% w/v sodium bromide solution as shown with respect to Table II. This resulted in a two-phase system with the tin halide complex below the aqueous solution and an interface between the two phases approximately 1 cm above the cathode plate 47. Sodium hydroxide aqueous solution (25%, 2l) at 51, 52 and 5
3 into the anode compartment formed by . The cell contents were heated to 75-95° and current was passed through both rectifiers. A total of 1103 amp-hours were passed through the nickel anode and 1163 amp-hours were passed through the tin anode. 5～
150 amperes (each 5.5mA/cm3~167
A current in the range of aqueous-non-aqueous interfacial current density (mA/cm3) was passed throughout this electrolysis, and the relative currents passed through the tin and nickel anodes were such that they gave approximately the same number of coulombs through each anode system. adjusted to. The starting cell voltage was about 20 volts, but this voltage tapered off to about 8-10 volts during electrolysis.

The electrolysis product is a 30% w/v sodium bromide solution 1
7.7 liters and 24 kg of a mixture of Bu4N+Br--dendritic tin-tin halide by-product. Tin anode is tin2
．． I lost a total of 57 kg.

For relatively high volume production, in addition to the cell shown in FIG. 3, the cell structures shown in FIGS. 4, 5 and 6 are currently preferred.

FIG. 4 shows a cross-sectional view of a 2000 amp cell, which would be equipped with conventional rectifiers, controls, etc. (not shown). In general, the structure of this cell is similar to that of FIG. However, in this example a polypropylene body 60 is supported by a mild steel casing 61 which is in turn positioned over load cells 62 (only one shown) which are held on a support platform. do. Similar to the apparatus of FIG. 3, a steel support structure 63 holds two tin or other corrodible metal anodes 64 (one shown) and a drive motor 65. The agitator drive may be a variable DC motor connected to the shaft 67 at 66;
This motor drives the lower agitator blade 68 and scraper blade 69. The top of the scraper blade also serves as a phase agitator. The scraper blade 69 satisfies the dual purpose of creating an upward flow movement of the metal halide complex to restore the electrolyte at the liquid-liquid interface, while removing precipitated metal from the cathode surface.

A push-in valve 70 is inserted into the bottom of the cone in the conical bottom of the cell to allow removal of metal dendrites and/or electrolyte from the cell.

Push-in valves are useful because, in the unlikely event that unstirred dendrite metal settles out and forms a crust, the crust can be cut open to allow evacuation of the upper phase.

Each metal anode 64 has a power of 100 to 200 k at startup, for example.
The insulated bushing structure 72 can have a weight of
It is held on a threaded steel rod 71 supported above. This structure and rod are respectively connected to the feeder cable 7.
Connected to 9. By this means the vertical position of the anode can be adjusted up or down.

The non-corrosive anode compartment is shown as 73 and is simply a polypropylene box with an open top and a bottom sealed by an ion exchange membrane with a suitable support and seal. . This anode chamber may be supported from the mild steel casing 61 by suitable steel parts 74 and into which is inserted a non-corrosive anode (not shown) connected to a power supply cable 75.

The cathode plates 74 are here two stainless steel semicircles supported on suitable polypropylene plugs in the cell and connected to the cathode cable 7.
8 (see Figure 7).

A suitable plate heater 80 may be suspended below the cathode plate. A cooling coil 76 is also placed within the cell and a cathode phase interface that is immiscible with the aqueous phase of the aqueous anolyte solution, although the level of the cathode plate may be varied depending on the most efficient operation of a given device. may be approximately 1 cm above the level of the cathode plate. For example, during full operation at 2000 amps and about 10 volts, the cooling coil 76 must be capable of removing about 20 KW.

to indicate the space or gap 77 between the cathodes to allow the metal particles of the dendrites to fall into the lower cone of the cell as they are removed by the scraper blade. , FIG. 6 is partially cut away. This gap may be about 2 cm wide, or even about 0.5 cm wide.
A spacing with a clearance of cm is maintained between the circumference of the cathode plate and the polypropylene cell body.

The capacity of this cell is, for example, configured to accommodate approximately 450 kg of tin halide complex by-product (as described above), approximately 500 liters of 10% sodium bromide solution, and approximately 100 liters of 25% sodium hydroxide solution for the nickel anode compartment 73. can be done,
Approximately 70-80° by constantly stirring everything
may be configured to be heated to.

Approximately 30 kg of NaOH during an operating period of approximately 20 hours at a current load of approximately 1500 faradays and 2000 amperes.
was consumed and slightly less than 90 kg of dendrite tin was produced, as well as about 120 kg of Bu4NBr and about 77 kg of dendrite tin.
kg of NaBr are produced. The loss of tin from the tin anode is slightly more than 44 kg, with the remainder of the dendritic tin resulting from decomposition of the tin halide complex.

It will be understood that the foregoing series of embodiments are merely illustrative of the implementation of the invention. That is, although tin is used as the metal anode to be corroded and is obtained as a dendritic cathode deposit, any of the other metals mentioned above may be used in place of tin.

Similarly, other Cat+ species can be used, and other halogens (eg, chlorine or iodine) can be used in place of bromine. To avoid complications from the formation of insoluble metal salt species, mineral acid anions, generally represented by X-, will of course be chosen. Alternatively, much the same method may be used using tin or one of the other metals, but using an organic carboxylic acid that is not itself substantially soluble in the aqueous phase as the catholyte, which is immiscible with the aqueous phase. . Furthermore,
Cat-species can be formed from alkali metal complexes or alkaline earth metal complexes using polyoxygen compounds or organic compounds such as diglyme, polyoxyalkylene glycols, glycol ethers or crown ethers.

In any given embodiment carried out in accordance with the present invention, the precise conditions to be used in anticipation of optimal results will be dictated by the various parameters employed in all equipment during the process. Therefore, the shape of the cell itself and the shape of the various electrodes, including the surface area of the electrolyte interface, will partially determine the performance and preferred operating conditions. As a result, the current density applied for optimal results will vary substantially from system to system. Therefore, exact guidelines cannot be stated in advance. However, once the foregoing principles are demonstrated in accordance with the present invention, each of these conditions can be easily determined, and one skilled in the art will be able to do so within the scope of the foregoing disclosure. The method already outlined can be easily adapted for any desired electrolytic reaction.

For example, it will be appreciated that the temperature of the system itself is not critical to the operational performance achieved, provided that the respective electrolytes are in liquid form and below any disadvantageous decomposition temperature. Of course, the interrelationships of temperature, applied current, concentration, and reaction rate may be optimized and otherwise varied widely for best results in any given system.

Therefore, the invention is limited only by the spirit and scope of the claims.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of a two-phase electrode cell using three electrodes and three electrolytes; Figure 2 is a diagram of a two-electrode two-phase system;
The figure is a schematic diagram showing a specific example of a cell using two electrodes and three types of electrolytes, and FIGS. 4 to 7 are diagrams showing specific examples using two cells. 11, 21, 47, 74... cathode, 13, 24...
Catholyte, 14, 16, 25, 34...Anolyte, 14a
...Liquid-liquid interface, 17, 18, 23, 33, 48, 5
0,64...Anode. Attorney attorney Imamura Original drawing of the original drawing Z (no change in content) Procedure Neil Seien 20 Name of invention Electric W? Electrolytic method using two phases that are electrically conductive; 3. Amendment 4/Relationship with Riru Personnel f'1 Name of applicant Mandenim Limited 4, Agent No. 1-14, Shinjuku 1, Shinjuku-ku, Tokyo
Yamaguchi 1 building, representative's column, drawings, and power of attorney (1) In the application, the inventor's address should be added as shown in the attached sheet. (2) Fill in the applicant's address and representative information in the application as shown in the attached sheet. (3) Official drawings will be added as shown in the attached sheet. (No change in content) (4) Supplement the power of attorney and its translation as shown in the attached document.

Claims (19)

[Claims] (1) An electrolysis method comprising passing an electric current between two electrodes through an at least two-phase electrolyte system, the electrolyte system comprising as a first phase an aqueous electrolyte solution;
It also includes a liquid immiscible with the aqueous phase conductive by the electrolyte with at least one electrode solely disposed therein as a second phase, the first and second phases being liquids. - said method, characterized in that the liquids are in direct mutual contact at the interface; (2) the first electrode is a corroded metal anode immersed solely in said first aqueous solution as an anolyte, and the second electrode is a corroded metal anode immersed solely in said first aqueous solution as a catholyte; 2. A method according to claim 1, characterized in that the inert cathode is solely immersed therein. 3. A method according to claim 2, characterized in that the anode to be corroded is made of tin. (4) The catholyte has the general formula RzQ+SnX-■ [However,
R is an organic group, Q represents N, P, As or Sb (in which case z is 4) or represents S or Se (in this case z is 3), and X is I, Cl or Br]. The method according to claim 3, wherein the halogenated stannite complex is 5. Process according to claim 3, characterized in that elemental tin is deposited on the cathode in the form of dendrites. (6) the first electrode is a non-corrosive anode immersed solely in the first aqueous anolyte, and the second electrode is an aqueous anolyte containing an at least partially ionic tin compound as the catholyte; an inert cathode immersed alone in a phase-immiscible liquid phase, whereby elemental tin is recovered from said tin compound in said aqueous phase-immiscible phase as said electric current is passed therethrough; A method according to claim 1, characterized in that: (7) The tin compound catholyte is general 2RzQ+SnX-3.
[However, R is an organic group, and Q is N, P, As or Sb
(in this case z is 4) or S or Se
(in which case z is 3) and X is I, Cl or Br]. . 8. Process according to claim 7, characterized in that tin is precipitated from the catholyte and deposited in the form of dendrites on the cathode. (9) The method according to claim 6, wherein the anode is made of nickel, graphite or stainless steel. (10) Containing two aqueous anolytes, a first anode is immersed in an alkali metal hydroxide anolyte, and this anolyte is simply passed through a cation-permeable membrane to a second aqueous anolyte. 2. A method according to claim 1, characterized in that the method is in contact with: (11) Claim 10, wherein the second anolyte is an aqueous solution of an alkali metal halide.
The method described in section. 12. The method of claim 10, wherein a second corroded metal anode is placed solely in the second anolyte. (13) A patent claim characterized in that one electrode is a corroding anode disposed solely in an aqueous phase, and the other electrode is a non-corroding cathode disposed solely in a non-aqueous phase. The method described in Scope No. 1. (14) The electrolyte immiscible with the aqueous phase is a cobalt or nickel salt of the carboxylic acid in a long-chain organic carboxylic acid, and one electrode used as an anode is formed of cobalt or nickel and the aqueous phase The other electrode, which is placed alone in a phase-immiscible electrolyte and is used as a cathode, is inert under the electrolytic conditions, and said cathode is placed alone in an aqueous solution of an alkyl metal salt of said carboxylic acid. Claim 1, characterized in that the cobalt or nickel from the anode is converted into its carboxylate salt, respectively, during said passage of electric current.
The method described in section. (15) one electrode is used as a non-corrosive anode, an aqueous solution of a soluble cobalt salt is used as the anolyte, and the other electrode is an inert cathode and is immiscible with the aqueous phase containing the water-insoluble cobalt salt; of the aqueous anolyte is used as the catholyte, whereby upon passing the current, cobalt ions are driven out of the aqueous anolyte and deposited as elemental cobalt on the cathode. The method described in Section 1. 16. The method of claim 2, wherein the metal anode to be corroded is formed from a metal having a standard electrode potential of about +1.5 volts to about -1.66 volts. . (17) The metal anode to be corroded is in the group consisting of silver, gold, platinum, palladium, copper, lead, tin, nickel, cobalt, indium, cadmium, iron, gallium, chromium, zinc, manganese, titanium, and aluminum. 3. A method according to claim 2, characterized in that the metal is formed from a metal of: (18) A method according to claim 1, characterized in that the organic compound is contained in a liquid immiscible with the aqueous phase and undergoes electrolytic reduction as a result of the passage of the electric current. . (19) The first corroded electrode is formed of cobalt metal or nickel metal and is in sole contact with the aqueous electrolyte as the anolyte, and the electrolyte is immiscible with the aqueous phase as the anolyte for a long time. A second inert electrode, consisting of a cobalt or nickel salt of a chain carboxylic acid and serving as a cathode, is in exclusive contact with the catholyte, so that upon passage of the electric current there is a droplet in the aqueous phase. A patent claim characterized in that the anode is corroded by providing cobalt ions or nickel ions, respectively, and these ions migrate into the catholyte and are precipitated at the cathode as elemental cobalt or elemental nickel, respectively. The method described in item 1 of the scope.